CN104817714A - Adamantane structure-containing polyarylether anion-exchange membrane and preparation method thereof - Google Patents

Abstract

Polyarylether anion exchange membrane containing adamantane structure and its preparation method. It relates to a chemical membrane separation material and a preparation method thereof. In the method, a polyarylether containing an adamantane structure is subjected to halomethylation modification to obtain a halomethylation containing an adamantane structure with a halomethylation degree of 10 to 200%. Polyarylether. The amination reaction of halomethylated polyarylether containing adamantane structure and nitrogen-containing organic small molecules is carried out to introduce anion exchange groups to prepare polyarylether anion exchange membrane containing adamantane structure. The prepared polyarylether containing adamantane structure Ether anion exchange membranes have high ion conductivity, excellent permeation selectivity and chemical stability, and can be used as diaphragms for all-vanadium flow energy storage batteries and alkaline fuel cells, with good application prospects.

Description

Polyarylether anion exchange membrane containing adamantane structure and preparation method thereof

technical field

The invention relates to a chemical membrane separation material and a preparation method thereof, in particular to an adamantane-containing polyarylether anion exchange membrane and a preparation method thereof.

Background technique

Anion exchange membranes can be used for electrodialysis concentrated seawater salt production, electrodialysis salt water desalination, industrial wastewater treatment, electrolysis, diffusion dialysis acid (alkali) recovery, fuel cells, liquid flow energy storage batteries and other new technology applications that require anion exchange membranes field. In all-vanadium redox flow energy storage batteries, the membrane is required to have high ion conductivity, excellent permeation selectivity and chemical stability. When commercial aryl polymers such as polysulfone and polyphenylsulfone have a high ion exchange capacity, the water content of the membrane is high, the swelling is severe, the dimensional stability and mechanical strength are reduced, and the stability of the membrane is poor. The rigid twisted structure and hydrophobic groups are introduced into the polymer to control the water content of the membrane and reduce the swelling of the membrane. Adamantane is a rigid cage-like saturated hydrocarbon with high thermal stability and strong hydrophobicity. Introducing adamantane into a polymer to obtain a rigid twisted structural unit increases the rigidity of the molecular chain, improves the thermal stability of the polymer, and enhances the polymer chain. Hydrophobicity, adjust the hydrophilic-hydrophobic balance of the membrane, and improve the stability of the membrane.

Contents of the invention

The object of the present invention is to provide a polyarylether anion exchange membrane containing an adamantane structure and a preparation method thereof. The method uses a polyarylether containing an adamantane structure as a raw material, and through halomethylation and amination, the anion exchange group The polyarylether containing adamantane structure is introduced into the polyarylether containing adamantane structure to prepare the polyarylether anion exchange membrane containing adamantane structure. The prepared polyarylether anion exchange membrane containing adamantane structure has high ion conductivity, excellent selective permeability and chemical stability.

The purpose of the present invention is achieved through the following technical solutions:

 The polyarylether anion exchange membrane containing adamantane structure is prepared by the steps of halomethylation and amination of polyarylether containing adamantane structure. The polymer molecular chain of polyarylether containing adamantane structure contains the following structure:

      

A method for preparing an anion-exchange membrane containing polyarylether with adamantane structure, comprising the following steps:

 The polyarylether containing adamantane structure is dissolved in the solvent, and the halomethyl alkyl ether and catalyst are added, and the reaction is stirred at a certain temperature. After the reaction, the reactant is poured into a precipitant, separated, washed and dried to obtain the halomethylated adamantane-containing polyarylether. The structural formula of halomethylated polyarylether containing adamantane structure is as follows:

      

Dissolving halomethylated polyarylene ether containing adamantane structure in a solvent to prepare a casting solution, casting a film, immersing the solvent in a precipitating agent after completely evaporating or partially evaporating, to obtain a halomethylated polyarylene containing adamantane structure ether-based film. The baking temperature of the halomethylated polyarylether base film containing adamantane structure is 10 o ^C -150 ^o C, and the time is 0-48 hours; the precipitant used is water, methanol, ethanol, propanol, isopropanol, acetone , ether, methyl ethyl ketone, ethyl acetate or a mixed solvent of two or more. Soaking the halomethylated polyarylether base membrane containing the adamantane structure in a nitrogen-containing organic small molecule solution for amination treatment to obtain the polyarylether anion exchange membrane containing the adamantane structure. The amination treatment temperature is 0 ^o C-90 ^o C, and the time is 0-96 hours.

The polyarylether anion exchange membrane containing adamantane structure can also be realized by the method of amination first and then membrane formation: the halomethylated polyarylether containing adamantane structure is dissolved in a solvent to prepare a solution, and nitrogen-containing organic small molecules are added to carry out Amination reaction, the reaction temperature is 0-90 ^o C, and the reaction time is 0-96 hours; the solution after the amination reaction is cast into a film, and the solvent is completely evaporated or partially evaporated and then immersed in a precipitant to obtain a polyarylene containing adamantane structure. For ether anion exchange membrane, the drying temperature is 10~150 ^o C, and the drying time is 0~48 hours.

The halomethyl alkyl ether used in the halomethylation modification of polyarylether containing adamantane structure in the present invention can be chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl butyl ether, chloromethyl Octyl ether, bromomethyl methyl ether, bromomethyl ethyl ether, bromomethyl butyl ether, bromomethyl octyl ether. The catalyst used for the halomethylation modification of polyarylether containing adamantane structure can be anhydrous zinc chloride, anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous zinc bromide, anhydrous ferric bromide, anhydrous Aluminum bromide in water, metal zinc powder, metal iron powder, metal aluminum powder, anhydrous tin tetrachloride, concentrated sulfuric acid, concentrated hydrochloric acid, phosphoric acid, chloroaluminate ionic liquid or trifluoromethanesulfonic acid or one or the above mixture of catalysts.

The solvent used for the halomethylation modification of polyarylether containing adamantane structure in the present invention can be chloroform, dichloromethane, dichloroethane, tetrachloroethane, nitrobenzene, chlorobenzene or concentrated sulfuric acid.

The reaction temperature of the halomethylation modification of polyarylether containing adamantane structure in the present invention is -10 o ^C -120 ^o C, and the reaction time is 1-72 hours.

The preparation of the halomethylated polyarylether-based film containing adamantane structure in the present invention can adopt chloroform, dichloromethane, dichloroethane, dimethylsulfoxide, N,N -dimethylformamide, N, N -dimethylacetamide, N -methyl-2-pyrrolidone or a mixed solution of the above solvents are solvents for preparing the casting solution.

The drying film temperature when preparing the cast film of halomethylated polyarylether containing adamantane structure according to the present invention can be 10-150 ^o C, preferably 30-120 ^o C, and the time is 0-48 hours, and the precipitating agent can be methanol , ethanol, water or one or a mixed solution of two solvents in the above solvents.

The reagents used in the amination treatment of halomethylated adamantane-containing polyarylethers described in the present invention can be nitrogen-containing organic small molecules, and the nitrogen-containing organic small molecules used can be trimethylamine, triethylamine, trimethylamine, triethylamine, or trimethylamine. One or a mixture of two or more of ethanolamine, tri-n-propylamine, tri-n-butylamine, pyridine, 1-methylimidazole, and 2-methylimidazole.

The amination treatment temperature of the halomethylated polyarylether containing adamantane structure in the present invention can be 0 ^° C-90 ^° C, and the time is 0-96 hours. The structure of polyarylether anion exchange membrane containing adamantane structure is as follows:

      

Advantage and effect of the present invention are:

The invention proposes to use polyarylether containing adamantane structure as raw material, and through halomethylation and amination, anion exchange groups are introduced into polyarylether containing adamantane structure to prepare polyarylether anion exchange membrane containing polyarylether with adamantane structure. The prepared polyarylether anion exchange membrane containing adamantane structure has high ion conductivity, excellent selective permeability and chemical stability, and has broad application in new technology fields requiring high-performance anion exchange membranes such as flow batteries and fuel cells. application prospects.

Detailed ways

The present invention will be described in detail below in conjunction with examples.

The examples list the preparation process and performance of the novel anion exchange membrane, these examples are only for illustrating the present invention, and are not intended to limit the protection scope of the present invention.

Example 1

Dissolve 5g of polyaryletherketone containing adamantane structure in 50mL of tetrachloroethane, heat up to 35 ^o C, add 1mL of tin tetrachloride, and then add 5mL of chloromethyl ether, react for 8 hours, pour the reaction solution into ethanol, the precipitated polymer was washed with a large amount of ethanol, and then dried in a vacuum oven at 70 ^o C to obtain a chloromethylated adamantane-containing polyarylether with a chloromethyl content of 2.3 mmol/g. The dried chloromethylated polyarylether containing adamantane structure is dissolved in N -methylpyrrolidone to prepare a casting solution with a polymer mass percentage of 10%. After filtering, pour the casting solution on a clean horizontal glass plate, scrape it into a film, and volatilize the solvent at 60 ^o C to obtain a base film with a thickness of 50 microns, and then soak it in water to further remove the solvent. The base membrane was placed in 33% trimethylamine aqueous solution, aminated at 50 ^o C for 72 hours, then transferred to 5% dilute hydrochloric acid, soaked for 2 hours, and then washed with deionized water to obtain an anion exchange membrane. The ion exchange capacity of this anion exchange membrane was 2.0 mmol/g.

Example 2

Dissolve 5g of polyaryletherketone containing adamantane structure in 50mL of tetrachloroethane, heat up to 50 ^o C, add 2mL of anhydrous tin tetrachloride, and then add 5mL of chloromethyl ether, and react for 10 hours. The solution was poured into ethanol, and the precipitated polymer was washed with a large amount of ethanol, and then dried in a vacuum oven at 70 ^o C to obtain a chloromethylated adamantane-containing polyarylether with a chloromethyl content of 2.1 mmol/g. The dried chloromethylated polyarylether containing adamantane structure is dissolved in N -methylpyrrolidone to prepare a casting solution with a polymer mass percentage of 10%. After filtering, scrape the casting solution on a clean horizontal glass plate to form a film, evaporate the solvent at 60 ^o C to obtain a base film with a thickness of 50 microns, and then soak it in water to further remove the solvent. Put the base film in 33% trimethylamine aqueous solution, and aminate it at 50 ^o C for 72 hours, then transfer the film to 5% dilute hydrochloric acid, soak it for 2 hours, and then wash it with deionized water to obtain polyarylene containing adamantane structure. ether anion exchange membrane. The ion exchange capacity of this anion exchange membrane was 1.9 mmol/g.

Example 3

An all-vanadium redox flow battery was assembled with the adamantane-containing polyaryletherketone anion exchange membrane in Example 1. The graphite felt was used as an electrode, and the graphite plate was used as a bipolar plate. The effective area of the membrane was 5 cm ² , and the current density was 100 mA/cm ^2. The concentration of vanadium ions in the electrolyte is 1.5 mol/L, and the concentration of H ₂ SO ₄ is 3 mol/L. The assembled vanadium redox flow battery has a current efficiency of 99%, a voltage efficiency of 83%, and an energy efficiency of 82%.

Example 4

An all-vanadium redox flow battery was assembled with the adamantane-containing polyaryletherketone anion exchange membrane in Example 2, the graphite felt was used as the electrode, the graphite plate was used as a bipolar plate, the effective area of the membrane was 5 cm ² , and the current density was 100 mA/cm ^2. The concentration of vanadium ions in the electrolyte is 1.5 mol/L, and the concentration of H ₂ SO ₄ is 3 mol/L. The assembled all-vanadium redox flow battery has a current efficiency of 99%, a voltage efficiency of 80%, and an energy efficiency of 79%.

comparative example

Compared with Examples 3 and 4, the membrane was replaced with a commercial Nafion117 membrane produced by DuPont, and other test conditions were the same. The current efficiency of the vanadium redox flow battery is 96%, the voltage efficiency is 80%, and the energy efficiency is 77%.

Compared with commercial Nafion membranes, the prepared adamantane-containing polyarylether anion exchange membranes have excellent resistance to vanadium, and are superior to Nafion membranes in current efficiency and energy efficiency, and the preparation cost of the membranes is much lower than that of perfluorinated membranes. The sulfonic acid-type Nafion membrane has good application prospects in the field of all-vanadium redox flow batteries.

The above description of the disclosed embodiments enables those skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. containing adamantane structure polyarylether anion-exchange membrane, it is characterized in that, described exchange membrane contains the polymer molecular chain of adamantane structure polyarylether containing, for example lower structure:

。

2. containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, described method comprises and is dissolved in solvent containing adamantane structure polyarylether, adds monochloromethyl alkyl oxide and catalyzer, reacts under stirring; After reaction terminates, reactant is poured in precipitation agent, separation, washing, drying, obtain halomethylation containing adamantane structure polyarylether; Skeleton symbol containing adamantane structure polyarylether is as follows:

；

Following preparation process is comprised containing adamantane structure polyarylether anionresin membrane preparation method:

Be dissolved in solvent containing adamantane structure polyarylether by halomethylation and be mixed with solution, casting film, after being evaporated completely by solvent or partly evaporating in immersion precipitation agent, obtain halomethylation containing adamantane structure polyarylether basement membrane, drying film temperature is 10 ~ 150 ^oc, drying the film time is 0 ~ 48 hour; Halomethylation is soaked in the solution of nitrogenous organic molecule containing adamantane structure polyarylether basement membrane and carries out amination treatment, obtain containing adamantane structure polyarylether anion-exchange membrane; Amination treatment temperature is 0 ~ 90 ^oc, the time is 0 ~ 96 hour;

Realize containing adamantane structure polyarylether anion-exchange membrane or by the method for masking after first amination: be dissolved in solvent containing adamantane structure polyarylether by halomethylation and be mixed with solution, add nitrogenous organic molecule and carry out amination reaction, temperature of reaction is 0 ~ 90 ^oc, the reaction times is 0 ~ 96 hour; Solution film casting after amination reaction, evaporates completely by solvent or in the rear immersion precipitation agent of part evaporation, obtain containing adamantane structure polyarylether anion-exchange membrane, drying film temperature is 10 ~ 150 ^oc, drying the film time is 0 ~ 48 hour;

Skeleton symbol containing adamantane structure polyarylether anion-exchange membrane is as follows:

。

3. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, the halomethylation modification monochloromethyl alkyl oxide containing adamantane structure polyarylether be chloromethyl methyl ether or for chloromethyl ether, chloromethyl butyl ether, chloromethyl octyl ether, bromomethyl methyl ether, brooethyl ether, the one of brooethyl butyl ether, brooethyl octyl ether.

4. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, be Zinc Chloride Anhydrous or the one for Anhydrous Ferric Chloride, Aluminum chloride anhydrous, Zinc Bromide Anhydrous, anhydrous iron bromide, ALUMINIUM BROMIDE ANHYDROUS, metal zinc, metal iron powder, metallic aluminium powder, anhydrous stannic chloride, the vitriol oil, phosphoric acid, chlorine Ion-selective electrod or trifluoromethane sulfonic acid containing the catalyzer that the halomethylation modification of adamantane structure polyarylether is used.

5. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, the halomethylation modification solvent for use containing adamantane structure polyarylether is chloroform, methylene dichloride, ethylene dichloride, tetrachloroethane, oil of mirbane, chlorobenzene or the vitriol oil; Precipitation agent used is one or more the mixed solvent in water, methyl alcohol, ethanol, propyl alcohol, ether, tetrahydrofuran (THF), acetone, butanone, ethyl acetate.

6. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, the temperature of reaction containing the halomethylation modification of adamantane structure polyarylether is-10 ^oc-120 ^oc, the reaction times is 1-72 hour.

7. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, with chloroform, methylene dichloride, ethylene dichloride, tetrachloroethane, dimethyl sulfoxide (DMSO), N, the mixing solutions of dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE or above-mentioned solvent is that the solvent preparing film-casting liquid prepares halomethylation containing adamantane structure polyarylether basement membrane.

8. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, preparing halomethylation containing the baking film temperature of adamantane structure polyarylether basement membrane is 30 ^oC-150 ^oc, time 0-48h.

9. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, the nitrogenous organic molecule that the amination reaction that halomethylation contains adamantane structure polyarylether adopts is one or more the mixture in Trimethylamine 99, triethylamine, trolamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, 1-Methylimidazole, glyoxal ethyline.

10. according to claim 2 containing adamantane structure polyarylether anionresin membrane preparation method, it is characterized in that, amination reaction temperature is 0 ^oC-90 ^oc, the time is 0-96 hour.